skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Growth of metal phthalocyanine on deactivated semiconducting surfaces steered by selective orbital coupling

Abstract

Using scanning tunneling microscopy and density functional theory, we show that the molecular ordering and orientation of metal phthalocyanine molecules on the deactivated Si surface display a strong dependency on the central transition-metal ion, driven by the degree of orbital hybridization at the heterointerface via selective p – d orbital coupling. As a result, this Letter identifies a selective mechanism for modifying the molecule-substrate interaction which impacts the growth behavior of transition-metal-incorporated organic molecules on a technologically relevant substrate for silicon-based devices.

Authors:
 [1];  [1];  [2];  [1];  [2];  [2]
  1. Michigan State Univ., East Lansing, MI (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1263862
Alternate Identifier(s):
OSTI ID: 1213101
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231; SC0006400
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 115; Journal Issue: 9; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Wagner, Sean R., Feng, Jiagui, Yoon, Mina, Zhang, Pengpeng, Huang, Bing, and Park, Changwon. Growth of metal phthalocyanine on deactivated semiconducting surfaces steered by selective orbital coupling. United States: N. p., 2015. Web. doi:10.1103/PhysRevLett.115.096101.
Wagner, Sean R., Feng, Jiagui, Yoon, Mina, Zhang, Pengpeng, Huang, Bing, & Park, Changwon. Growth of metal phthalocyanine on deactivated semiconducting surfaces steered by selective orbital coupling. United States. doi:10.1103/PhysRevLett.115.096101.
Wagner, Sean R., Feng, Jiagui, Yoon, Mina, Zhang, Pengpeng, Huang, Bing, and Park, Changwon. Tue . "Growth of metal phthalocyanine on deactivated semiconducting surfaces steered by selective orbital coupling". United States. doi:10.1103/PhysRevLett.115.096101. https://www.osti.gov/servlets/purl/1263862.
@article{osti_1263862,
title = {Growth of metal phthalocyanine on deactivated semiconducting surfaces steered by selective orbital coupling},
author = {Wagner, Sean R. and Feng, Jiagui and Yoon, Mina and Zhang, Pengpeng and Huang, Bing and Park, Changwon},
abstractNote = {Using scanning tunneling microscopy and density functional theory, we show that the molecular ordering and orientation of metal phthalocyanine molecules on the deactivated Si surface display a strong dependency on the central transition-metal ion, driven by the degree of orbital hybridization at the heterointerface via selective p – d orbital coupling. As a result, this Letter identifies a selective mechanism for modifying the molecule-substrate interaction which impacts the growth behavior of transition-metal-incorporated organic molecules on a technologically relevant substrate for silicon-based devices.},
doi = {10.1103/PhysRevLett.115.096101},
journal = {Physical Review Letters},
number = 9,
volume = 115,
place = {United States},
year = {2015},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Self-Assembly of Cobalt-Phthalocyanine Molecules on Epitaxial Graphene on Ir(111)
journal, September 2012

  • Hämäläinen, Sampsa K.; Stepanova, Mariia; Drost, Robert
  • The Journal of Physical Chemistry C, Vol. 116, Issue 38
  • DOI: 10.1021/jp306439h

Recent progress of molecular organic electroluminescent materials and devices
journal, December 2002


Importance of molecular alignment for organic photovoltaic devices
journal, October 2010

  • Xu, Zong-Xiang; Roy, V. A. L.; Liu, Zeng-Tao
  • Applied Physics Letters, Vol. 97, Issue 16
  • DOI: 10.1063/1.3502598

Structural defects of the Si(111)√3×√3-B surface studied by scanning tunneling microscopy
journal, January 1996


Inducing and Viewing the Rotational Motion of a Single Molecule
journal, March 1998


CoPc adsorption on Cu(111): Origin of the C4 to C2 symmetry reduction
journal, October 2010

  • Cuadrado, Ramón; Cerdá, Jorge I.; Wang, Yongfeng
  • The Journal of Chemical Physics, Vol. 133, Issue 15
  • DOI: 10.1063/1.3502682

Theoretical Insights into Adsorption of Cobalt Phthalocyanine on Ag(111): A Combination of Chemical and van der Waals Bonding
journal, October 2013

  • Baran, Jakub D.; Larsson, J. Andreas
  • The Journal of Physical Chemistry C, Vol. 117, Issue 45
  • DOI: 10.1021/jp409127e

Tuning intermolecular interaction in long-range-ordered submonolayer organic films
journal, January 2009

  • Stadler, Christoph; Hansen, Sören; Kröger, Ingo
  • Nature Physics, Vol. 5, Issue 2
  • DOI: 10.1038/nphys1176

Electronic and magnetic properties of molecule-metal interfaces: Transition-metal phthalocyanines adsorbed on Ag(100)
journal, April 2012


Quantitative modeling of in situ x-ray reflectivity during organic molecule thin film growth
journal, August 2011


Formation of Highly Ordered Organic Molecular Thin Films on Deactivated Si Surfaces Studied by Scanning Tunneling Microscopy and Low Energy Electron Diffraction
journal, January 2014

  • Wagner, Sean R.; Zhang, Pengpeng
  • The Journal of Physical Chemistry C, Vol. 118, Issue 4
  • DOI: 10.1021/jp4099599

Chemical Fingerprints of Large Organic Molecules in Scanning Tunneling Microscopy: Imaging Adsorbate−Substrate Coupling of Metalloporphyrins
journal, August 2009

  • Buchner, Florian; Warnick, Karl-Georg; Wölfle, Thorsten
  • The Journal of Physical Chemistry C, Vol. 113, Issue 37
  • DOI: 10.1021/jp904680c

Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009


Self-Assembly and Orbital Imaging of Metal Phthalocyanines on a Graphene Model Surface
journal, June 2014

  • Järvinen, Päivi; Hämäläinen, Sampsa K.; Ijäs, Mari
  • The Journal of Physical Chemistry C, Vol. 118, Issue 24
  • DOI: 10.1021/jp504813v

Energetics of metal–organic interfaces: New experiments and assessment of the field
journal, March 2009

  • Hwang, Jaehyung; Wan, Alan; Kahn, Antoine
  • Materials Science and Engineering: R: Reports, Vol. 64, Issue 1-2
  • DOI: 10.1016/j.mser.2008.12.001

Orientation-dependent ionization energies and interface dipoles in ordered molecular assemblies
journal, February 2008

  • Duhm, Steffen; Heimel, Georg; Salzmann, Ingo
  • Nature Materials, Vol. 7, Issue 4
  • DOI: 10.1038/nmat2119

Scanning Tunneling Microscopy of Metal Phthalocyanines:  d 7 and d 9 Cases
journal, January 1996

  • Lu, Xing; Hipps, K. W.; Wang, X. D.
  • Journal of the American Chemical Society, Vol. 118, Issue 30
  • DOI: 10.1021/ja960874e

Symmetry reduction of metal phthalocyanines on metals
journal, December 2008


Conformational Adaptation and Electronic Structure of 2H-Tetraphenylporphyrin on Ag(111) during Fe Metalation
journal, February 2011

  • Di Santo, Giovanni; Castellarin-Cudia, Carla; Fanetti, Mattia
  • The Journal of Physical Chemistry C, Vol. 115, Issue 10
  • DOI: 10.1021/jp111151n

Adsorption of boron on Si(111): Its effect on surface electronic states and reconstruction
journal, September 1989


Systematics of Molecular Self-Assembled Networks at Topological Insulators Surfaces
journal, March 2015

  • Bathon, T.; Sessi, P.; Kokh, K. A.
  • Nano Letters, Vol. 15, Issue 4
  • DOI: 10.1021/nl5048434

Control of in-plane orientation of phthalocyanine molecular columns using vicinal Si(001)-(2×1)-H
journal, June 2001

  • Nakamura, Masakazu; Matsunobe, Takeshi; Tokumoto, Hiroshi
  • Journal of Applied Physics, Vol. 89, Issue 12
  • DOI: 10.1063/1.1373700

Energetics and Hierarchical Interactions of Metal–Phthalocyanines Adsorbed on Graphene/Ir(111)
journal, August 2013

  • Scardamaglia, Mattia; Struzzi, Claudia; Lizzit, Silvano
  • Langmuir, Vol. 29, Issue 33
  • DOI: 10.1021/la401850v

Growth dynamics of pentacene thin films: Real-time synchrotron x-ray scattering study
journal, May 2006


Molecular Nanocrystals on Ultrathin NaCl Films on Au(111)
journal, September 2010

  • Wang, Yongfeng; Kröger, Jörg; Berndt, Richard
  • Journal of the American Chemical Society, Vol. 132, Issue 36
  • DOI: 10.1021/ja105110d

Theoretical and experimental comparison of SnPc, PbPc, and CoPc adsorption on Ag(111)
journal, February 2010


Molecule–Substrate Coupling between Metal Phthalocyanines and Epitaxial Graphene Grown on Ru(0001) and Pt(111)
journal, June 2012

  • Yang, K.; Xiao, W. D.; Jiang, Y. H.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 26
  • DOI: 10.1021/jp304068a

Relationship between Crystalline Order and Exciton Diffusion Length in Molecular Organic Semiconductors
journal, March 2010

  • Lunt, Richard R.; Benziger, Jay B.; Forrest, Stephen R.
  • Advanced Materials, Vol. 22, Issue 11
  • DOI: 10.1002/adma.200902827

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Coverage-Dependent Structures of Cobalt−Phthalocyanine Molecules Adsorbed on Cu(001) Surface
journal, July 2010

  • Guo, Qinmin; Qin, Zhihui; Zang, Kan
  • Langmuir, Vol. 26, Issue 14
  • DOI: 10.1021/la1019907

Nucleation and evolution of zinc phthalocyanine thin films on the deactivated Si(111)-B 3 × 3 R30° surface
journal, December 2014


Splitting of d-orbitals in square planar complexes of copper(II), nickel(II) and cobalt(II)
journal, March 1979


Internal structure of copper(II)-phthalocyanine thin films on SiO2∕Si substrates investigated by grazing incidence x-ray reflectometry
journal, April 2006

  • Brieva, A. C.; Jenkins, T. E.; Jones, D. G.
  • Journal of Applied Physics, Vol. 99, Issue 7
  • DOI: 10.1063/1.2180399

Temperature and gate voltage dependent transport across a single organic semiconductor grain boundary
journal, August 2001

  • Chwang, Anna B.; Frisbie, C. Daniel
  • Journal of Applied Physics, Vol. 90, Issue 3
  • DOI: 10.1063/1.1376404

Communication: Influence of graphene interlayers on the interaction between cobalt phthalocyanine and Ni(111)
journal, February 2013

  • Uihlein, Johannes; Peisert, Heiko; Glaser, Mathias
  • The Journal of Chemical Physics, Vol. 138, Issue 8
  • DOI: 10.1063/1.4793523

Layer-selective epitaxial self-assembly of porphyrins on ultrathin insulators
journal, January 2006


Charge-transfer-induced structural rearrangements at both sides of organic/metal interfaces
journal, March 2010

  • Tseng, Tzu-Chun; Urban, Christian; Wang, Yang
  • Nature Chemistry, Vol. 2, Issue 5
  • DOI: 10.1038/nchem.591

Charged and metallic molecular monolayers through surface-induced aromatic stabilization
journal, February 2013

  • Heimel, G.; Duhm, S.; Salzmann, I.
  • Nature Chemistry, Vol. 5, Issue 3
  • DOI: 10.1038/nchem.1572

Scanning Tunneling Microscopy, Orbital-Mediated Tunneling Spectroscopy, and Ultraviolet Photoelectron Spectroscopy of Metal(II) Tetraphenylporphyrins Deposited from Vapor
journal, May 2001

  • Scudiero, L.; Barlow, Dan E.; Mazur, Ursula
  • Journal of the American Chemical Society, Vol. 123, Issue 17
  • DOI: 10.1021/ja0100726

Tailoring molecular layers at metal surfaces
journal, January 2010


Surface-Induced Orientation Control of CuPc Molecules for the Epitaxial Growth of Highly Ordered Organic Crystals on Graphene
journal, February 2013

  • Xiao, Kai; Deng, Wan; Keum, Jong K.
  • Journal of the American Chemical Society, Vol. 135, Issue 9
  • DOI: 10.1021/ja3125096

Surfaces and Interfaces of Nanoscale Silicon Materials
journal, January 2013


Probing the Electronic Properties of Individual MnPc Molecules Coupled to Topological States
journal, August 2014

  • Sessi, P.; Bathon, T.; Kokh, K. A.
  • Nano Letters, Vol. 14, Issue 9
  • DOI: 10.1021/nl5017893

Coverage-Driven Electronic Decoupling of Fe-Phthalocyanine from a Ag(111) Substrate
journal, May 2011

  • Gopakumar, T. G.; Brumme, T.; Kröger, J.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 24
  • DOI: 10.1021/jp2038619

Scanning tunneling microscope study of iron(II) phthalocyanine growth on metals and insulating surfaces
journal, February 2008


Anisotropic Crystalline Organic Step-Flow Growth on Deactivated Si Surfaces
journal, February 2013


Electronic states due to surface doping: Si(111)√3×√3B
journal, January 1990


Interaction of Cobalt(II) Tetraarylporphyrins with a Ag(111) Surface Studied with Photoelectron Spectroscopy
journal, January 2007

  • Lukasczyk, Thomas; Flechtner, Ken; Merte, Lindsay R.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 7
  • DOI: 10.1021/jp0652345

Electronic structure and bonding in metal phthalocyanines, Metal=Fe, Co, Ni, Cu, Zn, Mg
journal, June 2001

  • Liao, Meng-Sheng; Scheiner, Steve
  • The Journal of Chemical Physics, Vol. 114, Issue 22
  • DOI: 10.1063/1.1367374

Selective adsorption and electronic interaction of F 16 CuPc on epitaxial graphene
journal, December 2010


Structural Properties of Iron Phtalocyanines on Ag(111): From the Submonolayer to Monolayer Range
journal, March 2011

  • Bobaru, S. C.; Salomon, E.; Layet, J. -M.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 13
  • DOI: 10.1021/jp111715a

Molecule–substrate interaction channels of metal-phthalocyanines on graphene on Ni(111) surface
journal, March 2011

  • Dou, Weidong; Huang, Shuping; Zhang, R. Q.
  • The Journal of Chemical Physics, Vol. 134, Issue 9
  • DOI: 10.1063/1.3561398

Epitaxial growth of pentacene films on Cu(110)
journal, January 2004

  • Söhnchen, S.; Lukas, S.; Witte, G.
  • The Journal of Chemical Physics, Vol. 121, Issue 1
  • DOI: 10.1063/1.1760076

Electronic structure of copper phthalocyanine: A comparative density functional theory study
journal, April 2008

  • Marom, Noa; Hod, Oded; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 128, Issue 16
  • DOI: 10.1063/1.2898540

Site-specific electronic and geometric interface structure of Co-tetraphenyl-porphyrin layers on Ag(111)
journal, June 2010